US5695695A - Manufacture of polymer fibrids - Google Patents
Manufacture of polymer fibrids Download PDFInfo
- Publication number
- US5695695A US5695695A US08/561,303 US56130395A US5695695A US 5695695 A US5695695 A US 5695695A US 56130395 A US56130395 A US 56130395A US 5695695 A US5695695 A US 5695695A
- Authority
- US
- United States
- Prior art keywords
- polyester
- fibrids
- liquid jets
- jet
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/26—Formation of staple fibres
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
Definitions
- Polymer fibrids are pure fibers having an irregular fiber morphology which are not spinnable and cannot be further divided.
- The are composed of the crystallites and any amorphous fiber components and represent the smallest fiber units.
- the possible uses of these fibers have increased greatly in recent years. Apart from the conventional fields of use, such as in paper manufacture, further markets can be opened up by the recyclability of the products which is gaining increasing importance.
- Polymer fibrids of polyethylene (HDPE, LLDPE) and polypropylene (PP) are already known.
- the polymer fibrids are produced in the flash spinning process. In this process, the polymers are emulsified in a water/solvent mixture under pressure and with heating and the emulsion is sprayed into a vacuum. This causes the solvent to evaporate, the temperature drops greatly and the polymer is converted, with crystallization, into fibrids.
- Polymer fibrids of polyacrylonitrile (PAN) or polyaromatics and cellulose acetate are produced from prefabricated splittable fibers.
- the route for producing the fibrids is via films or spun fibers.
- the film is extruded, cut, drawn and mechanically fibrillated. Under the action of heat, the film is drawn to a multiple of its length.
- the orientation of the molecules has to be carried out at a temperature below the crystallite melting point. A significant increase in the tensile strength and a decrease in the elongation at break in the draw direction occur.
- Spun fibers are specially highly drawn (high modulus) to increase the tendency to split.
- fibrids The use of the fibrids depends essentially on the raw material properties of the starting polymers. In many cases, necessitated by the process, a certain hydrophilicity is a prerequisite for the possible uses. To open up new possible applications or to provide existing applications with new properties which increase the product value, fibrids of other polymers, particularly polyesters, would be desirable. Attempts to produce fibrids based on polyester by the processes described above did not lead to success. Mechanical fibrillation is ruled out owing to the crystallization of the film during its production in a separate step (fixing), so that, because of its crystallized state, it can no longer become splittable, while the spinning process cannot be economically carried out due to lack of suitable solvents.
- polymer fibrids having the features being of a length of from 0.1 to 5 mm as a result of injecting polyesters as a low-viscosity jet into a shear field formed by liquid jets.
- the polyester is torn apart by the liquid jets and formed into the fibrids by cooling, a crystallization and orientation.
- a process has surprisingly been found, by means of which fibrids based on polyester, preferably of a polyphthalate ester, can be produced for the first time.
- the fibrids have the desired fibril finenesses and shortness of from 0.1 to 5 mm in production.
- the fibrids of the invention comprise a polyester which is injected as a low-viscosity jet into a shear field formed by liquid jets, torn apart by the liquid jets and formed into fibrids by cooling, crystallization and orientation.
- the fibrids based on polyester which are produced have a specific surface area of from 1 to 10 m 2 /g and are dispersible in water without pretreatment.
- the melting point lies in the range 200°-260° C. with good long-term heat resistance.
- the process of the invention for producing fibrids based on thermoplastic polyesters starts out from the idea of heating the polyester at temperatures below its decomposition temperature between 100° C. and 450° C., in particular between 250° C. and 400° C., to give a viscous mass and tearing it apart.
- the polyester jet has, after it is heated, a viscosity below 200 pascal.second, preferably below 100 Pa.s.
- the low-viscosity polyester is, under a pressure of between 100 and 1000 bar, injected at high velocity in a jet free into an energy-rich shear field.
- the shear field is formed by liquid or gaseous spray jets which are directed at a center and impinge on the polyester jet with high kinetic energy at pressures between 100 and 1000 bar.
- the spray jets preferably comprise low-temperature liquified gases such as the inert gases nitrogen and argon. Water too can be used at pressures above 100 bar.
- the polyester torn apart in the shear field comprising liquid nitrogen jets forms fibrids on cooling, crystallization and orientation.
- the polyester melted in an extruder is sprayed free at a temperature of from 100° C. to 450° C. into the shear field through a nozzle which determines the polyester jet geometry.
- the spray pressure is at least 100 bar and, in terms of its maximum pressure of, for example, 1000 bar, is restricted only by technical and economical limits.
- the polyester jet immediately reaches the center of the shear field produced by a nozzle system.
- the nozzle system consists of flat jet or full jet nozzles which are arranged at an angle of from 30° to 150° to the polyester jet.
- the polyester jet is here torn apart by the energy of the shear field and at the same time greatly cooled.
- the kinetic energy of the atomization medium preferably a liquified inert gas, in particular nitrogen, and the great temperature difference of up to 650 K. effect such a strong stressing of the polyester that it disintegrates into fibrids.
- the fibrids formed collect at the bottom of the reaction chamber. They can be taken out through an opening in the reaction chamber.
- the nitrogen gas formed is conveyed through a filter and a cyclone via a fan into a stack and thus into the open or into a recovery circuit.
- the nitrogen required by the nozzle system of the shear field reaches the nozzle system in the liquid state and under high pressure via a high-pressure pump from an insulator tank.
- the fibrids produced have significant variations in density and length of the individual fibrils and have a free surface area below that of products produced via an emulsion or by surface-dissolution. They have more covered surfaces.
- the controllability of the fibril sizes is significantly extended by the process of the invention, so that a very fine pulp can be achieved.
- Polyalkylene terephthalates belong to the group of polyphthalate esters. Two different types of polyalkylene terephthalates are polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). At room temperature, PET and PBT are hard, stiff, partially crystalline polymers which have good impact toughness even at low temperatures and have good sliding and abrasion behavior. PTP has very low viscosity at higher processing temperatures.
- RT 40 A low-viscosity PTP grade from Hoechst AG (RT 40) was broken up into fibrids in a shear field using low-temperature liquified nitrogen.
- RT 40 The physical properties of RT 40 are shown below:
- the experiments result in fibrids having fiber lengths of ⁇ 5 mm and a high temperature resistance. In addition, they have an extremely fine fiber structure with a lustrous character and have a very low proportion of film and melt particles.
Abstract
The invention enables production of polymer fibrids comprising a polyester which is injected as a low-viscosity jet into a shear field formed by liquid jets, torn apart by the liquid jets and formed into fibrids having a fibril length of from 0.1 to 5 mm by cooling, crystallization and orientation.
Description
Polymer fibrids are pure fibers having an irregular fiber morphology which are not spinnable and cannot be further divided. The are composed of the crystallites and any amorphous fiber components and represent the smallest fiber units. The possible uses of these fibers have increased greatly in recent years. Apart from the conventional fields of use, such as in paper manufacture, further markets can be opened up by the recyclability of the products which is gaining increasing importance.
Polymer fibrids of polyethylene (HDPE, LLDPE) and polypropylene (PP) are already known. The polymer fibrids are produced in the flash spinning process. In this process, the polymers are emulsified in a water/solvent mixture under pressure and with heating and the emulsion is sprayed into a vacuum. This causes the solvent to evaporate, the temperature drops greatly and the polymer is converted, with crystallization, into fibrids.
A prerequisite for this is a certain minimum degree of crystallization and certain minimum crystallization rates of the polymer. Only polymers which are economically and technically soluble in normally available solvents, for example aliphatic hydrocarbons, are suitable for the spinning process. The process results in products which have to be subjected to further treatment.
Polymer fibrids of polyacrylonitrile (PAN) or polyaromatics and cellulose acetate are produced from prefabricated splittable fibers. The route for producing the fibrids is via films or spun fibers. The film is extruded, cut, drawn and mechanically fibrillated. Under the action of heat, the film is drawn to a multiple of its length. The orientation of the molecules has to be carried out at a temperature below the crystallite melting point. A significant increase in the tensile strength and a decrease in the elongation at break in the draw direction occur. Spun fibers are specially highly drawn (high modulus) to increase the tendency to split.
The use of the fibrids depends essentially on the raw material properties of the starting polymers. In many cases, necessitated by the process, a certain hydrophilicity is a prerequisite for the possible uses. To open up new possible applications or to provide existing applications with new properties which increase the product value, fibrids of other polymers, particularly polyesters, would be desirable. Attempts to produce fibrids based on polyester by the processes described above did not lead to success. Mechanical fibrillation is ruled out owing to the crystallization of the film during its production in a separate step (fixing), so that, because of its crystallized state, it can no longer become splittable, while the spinning process cannot be economically carried out due to lack of suitable solvents.
It is an object of the invention to provide new polymer fibrids.
This object is achieved by means of polymer fibrids having the features being of a length of from 0.1 to 5 mm as a result of injecting polyesters as a low-viscosity jet into a shear field formed by liquid jets. The polyester is torn apart by the liquid jets and formed into the fibrids by cooling, a crystallization and orientation.
A process has surprisingly been found, by means of which fibrids based on polyester, preferably of a polyphthalate ester, can be produced for the first time. The fibrids have the desired fibril finenesses and shortness of from 0.1 to 5 mm in production.
The fibrids of the invention comprise a polyester which is injected as a low-viscosity jet into a shear field formed by liquid jets, torn apart by the liquid jets and formed into fibrids by cooling, crystallization and orientation. The fibrids based on polyester which are produced have a specific surface area of from 1 to 10 m2 /g and are dispersible in water without pretreatment. The melting point lies in the range 200°-260° C. with good long-term heat resistance.
The process of the invention for producing fibrids based on thermoplastic polyesters starts out from the idea of heating the polyester at temperatures below its decomposition temperature between 100° C. and 450° C., in particular between 250° C. and 400° C., to give a viscous mass and tearing it apart. The polyester jet has, after it is heated, a viscosity below 200 pascal.second, preferably below 100 Pa.s. The low-viscosity polyester is, under a pressure of between 100 and 1000 bar, injected at high velocity in a jet free into an energy-rich shear field. The shear field is formed by liquid or gaseous spray jets which are directed at a center and impinge on the polyester jet with high kinetic energy at pressures between 100 and 1000 bar. The spray jets preferably comprise low-temperature liquified gases such as the inert gases nitrogen and argon. Water too can be used at pressures above 100 bar. The polyester torn apart in the shear field comprising liquid nitrogen jets forms fibrids on cooling, crystallization and orientation.
The polyester melted in an extruder is sprayed free at a temperature of from 100° C. to 450° C. into the shear field through a nozzle which determines the polyester jet geometry. The spray pressure is at least 100 bar and, in terms of its maximum pressure of, for example, 1000 bar, is restricted only by technical and economical limits. There, the polyester jet immediately reaches the center of the shear field produced by a nozzle system. The nozzle system consists of flat jet or full jet nozzles which are arranged at an angle of from 30° to 150° to the polyester jet. The polyester jet is here torn apart by the energy of the shear field and at the same time greatly cooled. The kinetic energy of the atomization medium, preferably a liquified inert gas, in particular nitrogen, and the great temperature difference of up to 650 K. effect such a strong stressing of the polyester that it disintegrates into fibrids. The fibrids formed collect at the bottom of the reaction chamber. They can be taken out through an opening in the reaction chamber. The nitrogen gas formed is conveyed through a filter and a cyclone via a fan into a stack and thus into the open or into a recovery circuit. The nitrogen required by the nozzle system of the shear field reaches the nozzle system in the liquid state and under high pressure via a high-pressure pump from an insulator tank.
The fibrids produced have significant variations in density and length of the individual fibrils and have a free surface area below that of products produced via an emulsion or by surface-dissolution. They have more covered surfaces. The controllability of the fibril sizes is significantly extended by the process of the invention, so that a very fine pulp can be achieved.
Polyalkylene terephthalates (PTPs) belong to the group of polyphthalate esters. Two different types of polyalkylene terephthalates are polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). At room temperature, PET and PBT are hard, stiff, partially crystalline polymers which have good impact toughness even at low temperatures and have good sliding and abrasion behavior. PTP has very low viscosity at higher processing temperatures.
An extremely easy-flowing PTP type from Hoechst AG (Celanex) was divided into fibrids in a shear field using low-temperature liquified nitrogen. Celanex is a partially crystalline, thermoplastic polyester type based on PBT. PBT is produced by melt polycondensation of dimethyl terephthalate with 1,4-butanediol and has the following chemical formula: ##STR1##
The physical properties of Celanex are shown below:
______________________________________
Trade name: Celanex
Grade: 2000-2
Manufacturer: Hoechst AG
Melt index MVI 250/2: 65 cm.sup.3 /10 min
Density: 1.30 g/cm.sup.3
Crystallite melting range:
200-225° C.
______________________________________
Celanex was broken up under the experimental conditions given in the table:
______________________________________
PBT
Test material Celanex 2000
______________________________________
Temperature
Nozzle 340° C.
Zone 1 350° C.
Zone 2 300° C.
Zone 3 200° C.
Nitrogen nozzle Flat jet 1.02 mm
Polymer nozzle Full jet 0.47 mm
Nitrogen pressure 250 bar
Polymer pressure 180 bar
Spray time 4-5 sec
______________________________________
Sieve analysis:
______________________________________
Mesh opening in μm
PBT
______________________________________
800 93.6%
630 90.4%
400 77.6%
250 49.6%
______________________________________
The experiments result in fibrids having a (very) fine structure with a lustrous character.
A low-viscosity PTP grade from Hoechst AG (RT 40) was broken up into fibrids in a shear field using low-temperature liquified nitrogen. RT 40 is a partially crystalline, thermoplastic polyester type based on PET. PET is produced by melt polycondensation of dicarboxylic acids and dialcohols (=terephthalate acid+ethylene glycol=PET; RT 40 also contains a proportion of isophthalic acid) and has the following formula: ##STR2##
The physical properties of RT 40 are shown below:
______________________________________
Trade name: Impet
Grade: RT 40
Manufacturer: Hoechst AG
Density: 1.3 g/cm.sup.3
Crystallite melting range:
250-260° C.
______________________________________
Parameters:
______________________________________
Acid basis: terephthalic
and isophthalic acid
PET
Test material RT 40
______________________________________
Temperature
Nozzle 340° C.
Zone 1 350° C.
Zone 2 310° C.
Zone 3 200° C.
Nitrogen nozzle Flat jet 1.02 mm
Polymer nozzle Full jet 0.47 mm
Nitrogen pressure 250 bar
Polymer pressure 180 bar
Spray time 4-5 sec
______________________________________
Sieve analysis:
______________________________________
Mesh opening in μm
PET
______________________________________
800 100%
630 98.4%
400 95.2%
250 74.4%
______________________________________
The experiments result in fibrids having fiber lengths of ≦5 mm and a high temperature resistance. In addition, they have an extremely fine fiber structure with a lustrous character and have a very low proportion of film and melt particles.
Claims (12)
1. A process for forming polymer fibrids comprising injecting polyesters as a low-viscosity jet into a shear field formed by liquid jets, tearing apart the polyester by the liquid jets, and forming the polyester into fibrids having a fibril length of from 0.1 to 5 mm by cooling, a crystallization and orientation.
2. The process of claim 1 wherein the polymer fibrids are produced from a polyester jet having a viscosity below 200 Pa.s.
3. The process of claim 2 wherein the viscosity is below 100 Pa.s.
4. The process of claim 1 wherein the polyester is a polyterephthalate ester.
5. The process of claim 1 wherein the polyester is a polyalkylene terephthalate.
6. The process of claim 1 wherein the polyester is a polybutylene terephthalate.
7. The process of claim 1 wherein the liquid jets are formed from low-temperature liquified gases selected from the group consisting of nitrogen and argon.
8. The process of claim 1 wherein the liquid jets are sprayed at a pressure of between 10 and 600 bar onto the polyester jet.
9. In a process for forming polymer fibrids wherein the polymer fibrids are sprayed at a temperature below their decomposition temperature between 100° C. and 450° C. and at a pressure between 100 and 1000 bar into the shear field formed by liquid jets and are torn apart using liquid jets.
10. The process of claim 9 wherein the liquid jets are formed from low-temperature liquified gases selected from the group consisting of nitrogen and argon.
11. The process of claim 10 wherein the liquid jets are sprayed at a pressure of between 10 and 600 bar onto the polyester jet.
12. The process of claim 9 wherein the liquid jets are sprayed at a pressure of between 10 and 600 bar onto the polyester jet.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4441801.9 | 1994-11-24 | ||
| DE4441801A DE4441801C1 (en) | 1994-11-24 | 1994-11-24 | Polyesterfibride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5695695A true US5695695A (en) | 1997-12-09 |
Family
ID=6534016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/561,303 Expired - Fee Related US5695695A (en) | 1994-11-24 | 1995-11-21 | Manufacture of polymer fibrids |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5695695A (en) |
| EP (1) | EP0715007B1 (en) |
| JP (1) | JPH08209440A (en) |
| AT (1) | ATE176505T1 (en) |
| DE (1) | DE4441801C1 (en) |
| ES (1) | ES2131740T3 (en) |
| FI (1) | FI955640A (en) |
| ZA (1) | ZA959840B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6168733B1 (en) | 1998-08-31 | 2001-01-02 | Eastman Chemical Company | Method for forming discrete pellets from viscous materials |
| US6248267B1 (en) * | 1996-03-06 | 2001-06-19 | Mitsubishi Rayon Co., Ltd. | Method for manufacturing fibril system fiber |
| US10945381B1 (en) | 2014-07-02 | 2021-03-16 | Outdoor Product Innovations, Inc. | Modular tools with detachable coupling |
| US11306214B2 (en) | 2016-05-09 | 2022-04-19 | North Carolina State University | Fractal-like polymeric particles and their use in diverse applications |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19959532C1 (en) * | 1999-12-10 | 2001-10-04 | Seitz Schenk Filtersystems Gmb | Method and device for the production of filtration-active fibers |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2999788A (en) * | 1958-12-09 | 1961-09-12 | Du Pont | Synthetic polymer fibrid paper |
| DE1934541A1 (en) * | 1969-07-08 | 1971-01-14 | Basf Ag | Method and device for the production of staple fibers from thermoplastics |
| US4013744A (en) * | 1972-02-25 | 1977-03-22 | Badische Anilin- & Soda-Fabrik Aktiengesellschaft | Process for the manufacture of fibrids of thermoplastics materials |
| US4091058A (en) * | 1975-10-01 | 1978-05-23 | Basf Aktiengesellschaft | Manufacture of fibrids from poly(amide-imide) resins |
| US4112029A (en) * | 1973-12-21 | 1978-09-05 | Basf Aktiengesellschaft | Manufacture of fibrids of polyolefins |
| US4128614A (en) * | 1977-05-20 | 1978-12-05 | Celanese Corporation | Halogenated aromatic polyester fibers prepared via dry-spinning having reduced spin-line static generation |
| US4210615A (en) * | 1973-05-23 | 1980-07-01 | Basf Aktiengesellschaft | Manufacture of thermoplastics fibrids |
| US4219512A (en) * | 1976-10-14 | 1980-08-26 | Basf Aktiengesellschaft | Manufacture of fibrids from polymers |
| US4224259A (en) * | 1975-04-16 | 1980-09-23 | Basf Aktiengesellschaft | Manufacture of fibrids from polymers |
| EP0053188A1 (en) * | 1980-05-28 | 1982-06-09 | Toray Industries, Inc. | Heat retaining sheet |
| US4340442A (en) * | 1978-11-06 | 1982-07-20 | Champion International Corporation | Starch fibrids useful in enhancing the physical properties of paper, and process of preparing same |
| US4493751A (en) * | 1979-11-24 | 1985-01-15 | Hoechst Aktiengesellschaft | Polyoxymethylene fibrids, a process for their production and their use |
| US5482773A (en) * | 1991-07-01 | 1996-01-09 | E. I. Du Pont De Nemours And Company | Activated carbon-containing fibrids |
-
1994
- 1994-11-24 DE DE4441801A patent/DE4441801C1/en not_active Expired - Fee Related
-
1995
- 1995-11-02 EP EP95117219A patent/EP0715007B1/en not_active Expired - Lifetime
- 1995-11-02 AT AT95117219T patent/ATE176505T1/en not_active IP Right Cessation
- 1995-11-02 ES ES95117219T patent/ES2131740T3/en not_active Expired - Lifetime
- 1995-11-20 ZA ZA959840A patent/ZA959840B/en unknown
- 1995-11-21 JP JP7302674A patent/JPH08209440A/en active Pending
- 1995-11-21 US US08/561,303 patent/US5695695A/en not_active Expired - Fee Related
- 1995-11-23 FI FI955640A patent/FI955640A/en unknown
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2999788A (en) * | 1958-12-09 | 1961-09-12 | Du Pont | Synthetic polymer fibrid paper |
| DE1934541A1 (en) * | 1969-07-08 | 1971-01-14 | Basf Ag | Method and device for the production of staple fibers from thermoplastics |
| US4013744A (en) * | 1972-02-25 | 1977-03-22 | Badische Anilin- & Soda-Fabrik Aktiengesellschaft | Process for the manufacture of fibrids of thermoplastics materials |
| US4210615A (en) * | 1973-05-23 | 1980-07-01 | Basf Aktiengesellschaft | Manufacture of thermoplastics fibrids |
| US4112029A (en) * | 1973-12-21 | 1978-09-05 | Basf Aktiengesellschaft | Manufacture of fibrids of polyolefins |
| US4224259A (en) * | 1975-04-16 | 1980-09-23 | Basf Aktiengesellschaft | Manufacture of fibrids from polymers |
| US4091058A (en) * | 1975-10-01 | 1978-05-23 | Basf Aktiengesellschaft | Manufacture of fibrids from poly(amide-imide) resins |
| US4219512A (en) * | 1976-10-14 | 1980-08-26 | Basf Aktiengesellschaft | Manufacture of fibrids from polymers |
| US4128614A (en) * | 1977-05-20 | 1978-12-05 | Celanese Corporation | Halogenated aromatic polyester fibers prepared via dry-spinning having reduced spin-line static generation |
| US4340442A (en) * | 1978-11-06 | 1982-07-20 | Champion International Corporation | Starch fibrids useful in enhancing the physical properties of paper, and process of preparing same |
| US4493751A (en) * | 1979-11-24 | 1985-01-15 | Hoechst Aktiengesellschaft | Polyoxymethylene fibrids, a process for their production and their use |
| EP0053188A1 (en) * | 1980-05-28 | 1982-06-09 | Toray Industries, Inc. | Heat retaining sheet |
| US5482773A (en) * | 1991-07-01 | 1996-01-09 | E. I. Du Pont De Nemours And Company | Activated carbon-containing fibrids |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6248267B1 (en) * | 1996-03-06 | 2001-06-19 | Mitsubishi Rayon Co., Ltd. | Method for manufacturing fibril system fiber |
| US6168733B1 (en) | 1998-08-31 | 2001-01-02 | Eastman Chemical Company | Method for forming discrete pellets from viscous materials |
| US10945381B1 (en) | 2014-07-02 | 2021-03-16 | Outdoor Product Innovations, Inc. | Modular tools with detachable coupling |
| US11306214B2 (en) | 2016-05-09 | 2022-04-19 | North Carolina State University | Fractal-like polymeric particles and their use in diverse applications |
Also Published As
| Publication number | Publication date |
|---|---|
| FI955640A0 (en) | 1995-11-23 |
| EP0715007A1 (en) | 1996-06-05 |
| ZA959840B (en) | 1996-05-29 |
| DE4441801C1 (en) | 1996-06-05 |
| ATE176505T1 (en) | 1999-02-15 |
| FI955640A (en) | 1996-05-25 |
| ES2131740T3 (en) | 1999-08-01 |
| EP0715007B1 (en) | 1999-02-03 |
| JPH08209440A (en) | 1996-08-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: MESSER GRIESHEIM GMBH, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:STEINAU, PETER;JUNGERT, DIETER;MAI, VOLKER;AND OTHERS;REEL/FRAME:008711/0164;SIGNING DATES FROM 19951027 TO 19951114 |
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